Efficient water purification system

Abstract

The invention relates to the field of water pollution treatment, and discloses an efficient water purification system which comprises a reactor shell, an anode module, a cathode module, a sound field generation module, a light source module and a direct-current power supply module electrically connected with the anode module and the cathode module, and the anode module, the cathode module, the sound field generation module and the light source module are arranged in the reactor shell. The anode module is of a three-dimensional composite structure and integrates the functions of physical interception, adsorption enrichment and electrocatalytic oxidation; the cathode module is provided with a visible light response type catalytic layer, the catalytic layer can generate hydrogen peroxide in situ under illumination and cathode potential and generate strong oxidizing substances in cooperation with Fenton reaction, and the sound field generation module generates an ultrasonic sound field to strengthen the reaction mass transfer process. Through multi-path synergistic degradation and electrochemical and physical synergistic online regeneration, the pollutant removal efficiency is improved, the problem of electrode passivation is solved, and the stability of long-term operation of the system is guaranteed.

Description

Technical Field

[0001] This invention relates to the field of water pollution treatment technology, and in particular to a high-efficiency water purification system. Background Technology

[0002] With the acceleration of industrialization, the types and concentrations of organic pollutants in water bodies are increasing daily, including a large number of persistent organic pollutants that are difficult to biodegrade and have high chemical stability, posing a serious threat to the ecological environment and human health. Advanced oxidation technologies, due to their ability to generate hydroxyl radicals with extremely high oxidation potentials, can non-selectively mineralize recalcitrant organic pollutants into inorganic small molecules such as carbon dioxide and water, and are considered one of the most promising technologies for treating such polluted water bodies.

[0003] Among numerous advanced oxidation technologies, electrochemical advanced oxidation has attracted much attention due to its environmental friendliness, the absence of the need for additional chemical reagents, and the ease of automated equipment control. This technology primarily purifies water by directly oxidizing pollutants on the anode surface or indirectly oxidizing pollutants by generating hydroxyl radicals through anodic catalytic discharge of water molecules.

[0004] However, existing advanced electrochemical oxidation technologies still face several interconnected technical bottlenecks in practical applications, collectively restricting their purification efficiency and long-term operational stability. First, as a heterogeneous catalytic reaction, its overall reaction rate is largely limited by the mass transfer process of pollutant molecules from the bulk water to the catalytically active sites on the electrode. In traditional reactor configurations, the slow liquid-phase mass transfer efficiency often becomes the controlling step in the entire degradation process, preventing the intrinsic catalytic performance of the electrode from being fully utilized. More seriously, during long-term continuous operation, the electrode surface is highly susceptible to passivation due to the polymerization of pollutant degradation intermediates or the deposition of inorganic salts, leading to the covering or poisoning of the electrode's catalytically active sites. This electrode passivation phenomenon causes a continuous decline in system treatment efficiency and a significant increase in energy consumption, forcing frequent system shutdowns for offline cleaning or electrode replacement, greatly increasing operational complexity and maintenance costs. Furthermore, traditional electrochemical systems often rely on a single anodic oxidation pathway, which has limited degradation capacity for certain structurally stable pollutants with low reactivity. Although some studies have attempted to construct multiple oxidation systems, how to efficiently and synergistically generate multiple strong oxidizing species in a compact reactor and effectively avoid mutual interference between processes remains a technical challenge that urgently needs to be solved.

[0005] Therefore, developing a high-efficiency water purification system that can simultaneously enhance the mass transfer process, construct a multi-path synergistic oxidation system, effectively solve the electrode passivation problem, and achieve online recovery of electrode activity has significant practical implications and application value. Summary of the Invention

[0006] Existing water treatment technologies often suffer from technical problems when treating complex organic pollutants, such as low degradation efficiency, reaction rate limited by mass transfer, electrode passivation or fouling leading to deactivation, complex treatment processes, and the potential for secondary pollution.

[0007] To address the aforementioned technical problems, this invention provides a high-efficiency water purification system that integrates physical filtration, multi-field synergistic advanced oxidation, and online electrode self-cleaning functions.

[0008] The high-efficiency water purification system provided by this invention includes a reactor shell, an anode module, a cathode module, a DC power supply module, a sound field generation module, and a light source module.

[0009] The reactor shell defines a reaction space for containing the water to be treated and for housing the anode module, the cathode module, and the light source module.

[0010] The anode module, housed within the reactor shell, has an electrocatalyst loaded on its surface. The core function of this anode module is to degrade pollutants in the water through electrocatalytic oxidation.

[0011] In one specific embodiment, the anode module includes a three-dimensional porous conductive substrate unit, a three-dimensional graphene network unit, and a manganese dioxide nanocatalytic layer unit.

[0012] The three-dimensional porous conductive substrate unit (e.g., a foamed titanium substrate) serves as a large surface area current conduction framework and utilizes its porous structure to physically filter suspended matter in water.

[0013] The three-dimensional graphene network unit is coated on the surface of the three-dimensional porous conductive substrate unit by methods such as chemical vapor deposition. Its huge specific surface area is used to adsorb and enrich dissolved organic pollutants in water, while its excellent conductivity creates a highly efficient electron transport channel.

[0014] The manganese dioxide nanocatalytic layer unit is loaded onto the surface of the three-dimensional graphene network unit using techniques such as hydrothermal methods, constituting the electrocatalyst. Under the anodic potential applied by the DC power module, this catalytic layer unit can directly promote the oxidation of adsorbed pollutants (denoted as R) through electron transfer, and can also efficiently catalyze the decomposition of water molecules, generating highly oxidizing hydroxyl radicals (·OH) in situ. The related reaction process can be represented as follows:

[0015] Direct electron transfer: R→R ox +ne - ; Hydroxyl radical formation: H₂O → ·OH + H₂ + +e -; The cathode module, spaced apart from the anode module, is disposed within the reactor shell, and its surface is provided with a visible light-responsive catalytic layer. The core function of this cathode module is to synergistically perform electrochemical and photocatalytic reactions, further converting the intermediate products generated in the electrochemical reaction into strong oxidizing substances.

[0016] In one specific embodiment, the cathode module includes a Z-type heterojunction semiconductor catalytic layer unit and an in-situ Fenton catalytic center unit.

[0017] The Z-type heterojunction semiconductor catalyst layer unit (e.g., composed of graphitic carbon nitride and bismuth vanadate) constitutes the visible light responsive catalyst layer. Under the cathode potential applied by the DC power supply module, dissolved oxygen in the water undergoes an oxygen reduction reaction, generating hydrogen peroxide (H2O2) as an intermediate product. Simultaneously, under illumination from the light source module, the Z-type heterojunction semiconductor catalyst layer unit is excited to generate photogenerated electrons and holes. Its unique band structure enables efficient separation of photogenerated electron-hole pairs, and the photogenerated electrons, with their strong reducing power, promote the oxygen reduction reaction. The in-situ Fenton catalytic center unit (e.g., iron oxide nanoparticles supported on the catalyst layer surface) undergoes a highly efficient Fenton-like reaction with the intermediate product H2O2 generated by the above electrochemical reaction, generating hydroxyl radicals (·OH) as the strong oxidizing agent. Simultaneously, the cathode potential or photogenerated electrons can promote the regeneration of this catalytic center, achieving a catalytic cycle. The related reaction process can be represented as follows: Hydrogen peroxide is generated: O2 + 2H + +2e - →H2O2; Fenton-like reaction: Fe 2+ +H₂O₂→Fe 3+ +·OH+OH - ; Catalytic center regeneration: Fe 3 +e - →Fe 2+ The DC power supply module is electrically connected to the anode module and the cathode module respectively, providing driving power for the above electrochemical reaction.

[0018] In a preferred embodiment, the DC power module includes a pulse control unit that can output periodic positive oxidation pulses and reverse polarization pulses, the latter of which helps to strip passivation material from the electrode surface.

[0019] The acoustic field generating module, coupled to the reactor shell, is used to generate an ultrasonic acoustic field within the reaction space. This acoustic field, through high-speed microjets and shock waves generated by cavitation effects, can violently disturb the liquid-phase mass transfer boundary layer on the electrode surface, enhancing the transport of contaminants to the electrode active sites, thereby strengthening the overall electrochemical reaction process.

[0020] In a preferred embodiment, the sound field generating module includes an energy focusing control unit that can generate intermittent energy-focused sound fields to reduce energy consumption and improve sound energy utilization efficiency.

[0021] The light source module is disposed inside the reactor shell and is used to provide light of a specific wavelength to the visible light responsive catalytic layer of the cathode module to stimulate its photocatalytic activity.

[0022] In a particularly preferred embodiment, the system further includes a coordination control unit for controlling the sound field generation module and the DC power supply module to work together, so that the intermittent energy-focused sound field and the reverse polarization pulse are applied synchronously, thereby utilizing the physical stripping effect of the sound field during the electrode regeneration stage to achieve a better online electrode cleaning effect.

[0023] In summary, the present invention has at least one of the following beneficial technical effects: 1. This invention constructs two independent strong oxidation cores within the reactor through a specific anode and cathode module design. The anode module directly oxidizes pollutants and generates hydroxyl radicals in situ through electrocatalysis. Simultaneously, the cathode module converts hydrogen peroxide, an oxygen reduction product, into hydroxyl radicals through photo-electric synergy. This dual-core layout forms a three-dimensional, distributed oxidation capacity, which can more thoroughly mineralize complex organic matter in water bodies and effectively avoid the reaction dead zones or intermediate product accumulation problems that exist in single oxidation pathways.

[0024] 2. This invention generates an ultrasonic sound field in the reactor through a sound field generation module. The cavitation effect violently disturbs the mass transfer boundary layer on the electrode surface, transporting pollutant molecules to the catalytic active sites at high speed. This overcomes the mass transfer limitations of traditional electrochemical methods, thereby significantly improving the reaction rate. On the other hand, the physical impact force of the sound waves can continuously peel off the passivation layer or contaminants that are easily formed on the electrode surface, realizing online self-cleaning of the electrodes and ensuring the long-term, efficient, and stable operation of the system.

[0025] 3. The anode module of this invention integrates physical filtration, adsorption enrichment and electrocatalytic oxidation functions, enabling raw water to undergo multi-stage purification within a single module. This simplifies the overall process flow and transforms the low-value-added cathode hydrogen evolution process in traditional electrolysis reactions into an in-situ process of generating hydrogen peroxide and using it as a Fenton reaction reagent, thereby greatly improving the atom economy of the cathode reaction and the overall energy utilization efficiency of the system. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the architecture of a high-efficiency water purification system according to an embodiment of the present invention; Figure 2 This is a flowchart illustrating the operation of a high-efficiency water purification system according to an embodiment of the present invention. Detailed Implementation

[0027] The following is in conjunction with the appendix Figure 1 With appendix Figure 2 The present invention will be further described in detail below.

[0028] See attached document Figure 1 , Figure 1 This is a schematic diagram of the architecture of a high-efficiency water purification system 100 according to an embodiment of the present invention. In a specific embodiment, the high-efficiency water purification system 100 provided by the present invention includes six core modules: reactor shell 10, anode module 20, cathode module 30, DC power supply module 40, sound field generating module 50, and light source module 60.

[0029] The reactor shell 10 defines a reaction space for containing the water to be treated. The reactor shell 10 also physically supports the anode module 20, cathode module 30, and light source module 60. The reactor shell 10 is provided with an inlet and an outlet to establish a flow path for the water to be treated.

[0030] Both the anode module 20 and the cathode module 30 are disposed within the reaction space defined inside the reactor shell 10. The anode module 20 and the cathode module 30 are arranged at intervals with a preset electrode spacing, for example, by using a parallel plate structure fixed within the insulating frame of the reactor shell 10.

[0031] A DC power supply module 40 is disposed outside the reactor shell 10 and is electrically connected to the positive terminal of the anode module 20 and the negative terminal of the cathode module 30 via wires. The DC power supply module 40 is used to provide the electrical energy required to drive the electrochemical reaction in the anode module 20 and the cathode module 30.

[0032] The acoustic field generating module 50 is mechanically coupled to the reactor shell 10. In one particular layout, the acoustic field generating module 50 (e.g., an ultrasonic transducer array) is attached to the outer wall of the reactor shell 10 and its acoustic field radiation direction is directed towards the reaction space inside the reactor shell 10, so as to ensure that the generated ultrasonic acoustic field can effectively act on the water to be treated, especially on the surface of the anode module 20, to enhance the mass transfer process.

[0033] The light source module 60 is disposed inside the reactor shell 10. The mounting position of the light source module 60 enables it to provide uniform illumination to the visible light responsive catalyst layer surface of the cathode module 30, thereby stimulating the photocatalytic activity of the cathode module 30.

[0034] In one specific embodiment, the reactor housing 10 is made of a material with high light transmittance and chemical stability, such as quartz glass or polymethyl methacrylate (PMMA). The light-transmitting material is chosen to ensure that the light emitted by the light source module 60 disposed inside the reactor housing 10 can effectively penetrate the wall of the reactor housing 10 and illuminate the surface of the cathode module 30.

[0035] The reactor shell 10 has an internal hollow structure for accommodating the water to be treated, which defines the reaction space where the system performs the purification reaction. The shell wall of the reactor shell 10 is provided with an inlet and an outlet for connecting to external fluid pipelines to achieve continuous flow or batch processing of the water to be treated within the reaction space.

[0036] Inside the reactor shell 10, an insulating fixing frame is provided for fixing the anode module 20 and the cathode module 30. The insulating fixing frame is made of electrically insulating and corrosion-resistant materials such as polytetrafluoroethylene (PTFE) or polyether ether ketone (PEEK). Its structural design is used to ensure that the anode module 20 and the cathode module 30 maintain a stable, parallel relative position and a preset electrode spacing in the reaction space, and to prevent physical contact between them from causing a short circuit.

[0037] On the outer wall of the reactor shell 10, one or more flat contact surfaces are provided for coupling with the sound field generating module 50. The design of this contact surface is intended to ensure good acoustic coupling between the sound field generating module 50 and the reactor shell 10, so as to reduce the attenuation of ultrasonic energy at the interface and enable the ultrasonic sound field to be efficiently transmitted into the reaction space.

[0038] The anode module 20 is a three-dimensional composite electrode structure, which includes, from the inside out: a three-dimensional porous conductive substrate unit, a three-dimensional graphene network unit, and a manganese dioxide nanocatalytic layer unit.

[0039] In one specific embodiment, the three-dimensional porous conductive substrate unit is a foamed titanium substrate. This foamed titanium substrate has a three-dimensionally interconnected porous structure with a pore size ranging from 100 to 500 micrometers and a porosity of 85% to 95%. This unit serves as a conductive framework in the anode module 20, providing mechanical support and current collection channels for the entire module. Its porous structure also allows the water to be treated to permeate and flow within it, thereby physically filtering and intercepting suspended particulate matter in the water. Before use, the foamed titanium substrate is pretreated, for example, by acid washing in hydrochloric acid or oxalic acid solutions, to remove the oxide layer on its surface and increase surface roughness, thereby improving the adhesion of subsequent functional layers.

[0040] Three-dimensional graphene network units were prepared by chemical vapor deposition (CVD) and coated onto the entire framework surface of a three-dimensional porous conductive substrate unit. Using methane as the carbon source, graphene was grown in situ on the surface of a titanium foam substrate under high temperature and an inert atmosphere, forming a continuous, complete, and tightly bonded three-dimensional graphene network. The functions of this unit are: firstly, utilizing the enormous specific surface area of ​​graphene, it provides numerous adsorption sites for the adsorption and enrichment of dissolved organic pollutants in water; secondly, utilizing the excellent conductivity of graphene, it constructs a highly efficient electron transport network between the three-dimensional porous conductive substrate unit and the subsequently supported manganese dioxide nanocatalyst layer unit.

[0041] Manganese dioxide nanocatalytic layer units are loaded onto the surface of three-dimensional graphene network units via hydrothermal synthesis, and these units constitute the electrocatalyst. A foamed titanium substrate with a three-dimensional graphene network is immersed in a hydrothermal reactor containing precursor salts such as potassium permanganate (KMnO4) and reacted for several hours at a specific temperature (e.g., 120-180℃). This allows manganese dioxide to grow in situ in the form of nanosheets or nanowires and be uniformly loaded onto the surface of the three-dimensional graphene network. This unit is the core active part of the electrocatalytic oxidation. Under the anodic potential applied by the DC power module 40, its surface can not only directly initiate electron transfer of enriched pollutants but also efficiently catalyze the decomposition of water molecules, generating highly oxidizing hydroxyl radicals (·OH) in situ.

[0042] The cathode module 30 includes a conductive substrate (e.g., carbon cloth, carbon felt, or FTO conductive glass) and a functional composite layer disposed on the surface of the conductive substrate, forming a visible light responsive catalytic layer. Specifically, the functional composite layer includes a Z-type heterojunction semiconductor catalytic layer unit and an in-situ Fenton catalytic center unit.

[0043] In one specific embodiment, the Z-type heterojunction semiconductor catalyst layer unit is composed of graphitic carbon nitride (g-C3N4) and bismuth vanadate (BiVO4). Its preparation method, for example, employs a layer-by-layer deposition method: firstly, a layer of bismuth vanadate is uniformly grown on the surface of a conductive substrate by electrodeposition or hydrothermal methods; subsequently, a graphitic carbon nitride nanosheet dispersion, pre-prepared through high-temperature thermal polymerization (e.g., using melamine or urea as a precursor), is coated onto the surface of the bismuth vanadate layer by spin coating or dip-coating. After drying and curing, the two form a tight Z-type heterojunction interface.

[0044] The function of this Z-type heterojunction semiconductor catalyst layer unit is that when the light source module 60 provides visible light irradiation, both semiconductors (g-C3N4 and BiVO4) are excited to generate photogenerated electrons (e-C3N4 and BiVO4). - ) and photogenerated holes (h + Based on the band structure of the Z-type heterojunction, electrons in the conduction band of g-C3N4 with a lower reduction potential recombine with holes in the valence band of BiVO4 with a higher oxidation potential. This allows photogenerated electrons with strong reducing power to remain in the conduction band of BiVO4, while photogenerated holes with strong oxidizing power remain in the valence band of g-C3N4. This achieves efficient spatial separation of photogenerated carriers and maintains their high reactivity.

[0045] The in-situ Fenton catalytic center unit consists of iron oxide nanoparticles (e.g., α-Fe₂O₃ or FeOOH) supported on the surface of a type 2 heterojunction semiconductor catalyst layer unit. Preparation methods include, for example, impregnation-calcination: the prepared Z-type heterojunction semiconductor catalyst layer is immersed in an ethanol or aqueous solution containing iron salts (e.g., Fe(NO₃)₃), and after a period of immersion, it is removed, dried, and calcined at high temperature, allowing the iron oxide nanoparticles to be anchored in situ on the surface of the semiconductor catalyst layer in a highly dispersed form. During system operation, the DC power module 40 provides a continuous cathode potential to the cathode module 30. This potential drives dissolved oxygen (O₂) in the water to undergo a two-electron pathway oxygen reduction reaction (ORR) on the cathode surface, generating hydrogen peroxide (H₂O₂) as an intermediate product of the electrochemical reaction. This process can be represented as: O2 + 2H + +2e - →H2O2; Subsequently, the in-situ Fenton catalytic central unit (in Fe) supported on the surface 3+ / Fe 2+ (Taking a cycle as an example) The in-situ generated H2O2 immediately undergoes a Fenton-like reaction, efficiently generating hydroxyl radicals (·OH), which are strong oxidizing agents. This process can be represented as: Fe 2+ +H₂O₂→Fe 3+ +·OH+OH- ; During this process, the highly active photogenerated electrons (such as electrons retained in the conduction band of BiVO4) generated by the Z-type heterojunction excited by the light source module 60, as well as the electrons provided by the cathode potential itself, can both convert the Fe generated in the Fenton-like reaction into Fe. 3+ Rapid reduction and regeneration to Fe 2+ To achieve continuous cyclic regeneration of the Fenton catalytic center, the regeneration process can be represented as: Fe 3+ +e - →Fe 2 + ; Through the synergistic effects of light, electricity, and catalysis, the cathode module 30 achieves in-situ generation, in-situ catalytic decomposition, and catalyst regeneration cycle of H2O2, thereby continuously generating hydroxyl radicals (·OH).

[0046] In one specific embodiment, the DC power module 40 is a programmable electrochemical workstation or DC power supply. Its output terminals are electrically connected to the anode module 20 and the cathode module 30 via wires, respectively, to provide driving power for the electrochemical reactions in the entire high-efficiency water purification system 100. The DC power module 40 can operate in constant voltage (potential constant method) or constant current (current constant method) mode.

[0047] In a preferred embodiment, the DC power module 40 includes a pulse control unit. This pulse control unit is a microprocessor or programmable logic controller used to precisely control the DC power module 40 to output a periodic sequence of voltage or current pulses. Specifically, the pulse sequence includes forward oxidation pulses and reverse polarization pulses.

[0048] The forward oxidation pulse is the main pulse applied during the system's pollutant degradation process. During this pulse, the DC power module 40 applies a preset positive potential (or outputs a preset forward current) to the anode module 20 to drive the electrocatalytic oxidation of pollutants and the decomposition of water molecules to produce hydroxyl radicals on the surface of the anode module 20. Simultaneously, it drives the oxygen reduction reaction on the surface of the cathode module 30 to generate hydrogen peroxide. The duration of this forward oxidation pulse is relatively long, for example, set to 5 to 30 minutes.

[0049] A reverse polarization pulse is a short pulse periodically inserted between forward oxidation pulses. During this pulse, the pulse control unit controls the DC power supply module 40 to briefly reverse the potential polarity applied to the two electrodes, i.e., the original anode module 20 becomes the cathode, and the original cathode module 30 becomes the anode. The purpose of this reverse polarization pulse is to utilize electrochemical reduction or electrochemical oxidation to strip or decompose passivation substances or contaminant byproducts accumulated on the electrode surface during long-term operation, thereby achieving online recovery of electrode activity. The duration of this reverse polarization pulse is short, for example, set to 10 to 60 seconds.

[0050] In one specific embodiment, the sound field generating module 50 is specifically one or more sets of piezoelectric ceramic ultrasonic transducers. The sound field generating module 50 is mechanically coupled and closely attached to a specific location on the outer wall of the reactor shell 10, and through an acoustic coupling medium or a high-pressure fastening structure, it ensures that ultrasonic energy can be radiated and transmitted efficiently to the reaction space inside the reactor shell 10 with minimal attenuation.

[0051] The sound field generating module 50 is set to operate at a specific ultrasonic frequency, such as a frequency in the range of 20kHz to 100kHz. Driven by this frequency, the sound field generating module 50 generates a high-intensity ultrasonic sound field in the water to be treated within the reaction space, which induces the acoustic cavitation effect of the liquid.

[0052] The high-speed microjets and shock waves released by the collapse of cavitation bubbles generated by acoustic cavitation can continuously and violently disturb the liquid mass transfer boundary layer on the surfaces of the anode module 20 and the cathode module 30, greatly accelerating the transport rate of pollutant molecules from the water to the electrode catalytic active sites, thereby enhancing the overall efficiency of the electrochemical reaction process.

[0053] In a preferred embodiment, the sound field generating module 50 includes an energy focusing control unit. This energy focusing control unit is essentially a programmable ultrasonic generator controller electrically connected to the ultrasonic transducer.

[0054] This energy focusing control unit is used to precisely control the ultrasonic transducer to operate in a discontinuous pulse mode, i.e., to generate an intermittent energy-focused sound field. Specifically, the unit controls the ultrasonic waves to be output according to a preset duty cycle, such as setting a cycle (e.g., 3 seconds), which includes an on-time (e.g., 1 second) and an off-time (e.g., 2 seconds). This intermittent application reduces the average energy consumption required to maintain the sound field; on the other hand, it allows cavitation bubbles sufficient time to grow to their maximum size during the off-time, and then instantaneously collapses under the sound pressure of the next on-time, thereby achieving a concentrated release of sound energy at a specific point in time and increasing the instantaneous intensity of the acoustic cavitation effect.

[0055] In one specific embodiment, the light source module 60 is a waterproof array of light-emitting diodes (LEDs) or a cold cathode fluorescent lamp. The light source module 60 is installed in the reaction space inside the reactor shell 10 and is fixed by an insulating fixing frame inside the reactor shell 10.

[0056] The physical installation position of the light source module 60 is set so that its emitting surface faces the visible light responsive catalyst layer surface of the cathode module 30, and maintains a preset distance from the surface. This arrangement is used to ensure that the light emitted by the light source module 60 can directly and uniformly irradiate the catalyst layer surface of the cathode module 30, thereby providing the required photon energy for the photocatalytic reaction.

[0057] The emission spectrum characteristics of the light source module 60 are selected to match the optical absorption spectrum range of the Z-type heterojunction semiconductor catalyst layer unit of the cathode module 30. For example, when the catalyst layer of the cathode module 30 is composed of graphitic carbon nitride and bismuth vanadate composite, the light source module 60 is selected as a visible light source with an emission wavelength range covering 400 nm to 700 nm to ensure that the semiconductor catalyst layer unit can efficiently absorb light energy and be excited to generate photogenerated electron-hole pairs.

[0058] The light source module 60 is electrically connected to an external drive power supply through a waterproof wire passing through the sealed interface of the reactor shell 10. This drive power supply provides the voltage and current required for the stable operation of the light source module 60.

[0059] See attached document Figure 2 , Figure 2 This is a flowchart illustrating the operation of a high-efficiency water purification system according to an embodiment of the present invention. The embodiment of the present invention provides a method for operating a high-efficiency water purification system 100, which may include the following steps: S100: The water to be treated is introduced into the reaction space inside the reactor shell 10 through the inlet until the water to be treated completely submerges the anode module 20 and the cathode module 30.

[0060] S200: The DC power supply module 40 is activated, applying a preset positive oxidation pulse between the anode module 20 and the cathode module 30, thereby establishing a stable electric field between them. Simultaneously, the light source module 60 is activated, illuminating the surface of the cathode module 30. The sound field generating module 50 is also activated, generating a high-intensity ultrasonic sound field within the reaction space.

[0061] S300: Under the synergistic effect of the aforementioned electric, light, and acoustic fields, pollutants in the water to be treated begin to degrade. The water remains in the reaction space for a preset time in a continuous flow or batch treatment manner to ensure that pollutants are fully removed.

[0062] S400: In a preferred embodiment, after the system has been running continuously for a preset time period, an online electrode regeneration step is performed. The pulse control unit within the DC power module 40 controls it to stop outputting forward oxidation pulses and switches to outputting shorter-duration reverse polarization pulses to the anode module 20 and the cathode module 30.

[0063] S500: Specifically, when the system is equipped with a co-control unit, the co-control unit controls the sound field generating module 50 to work in conjunction with the DC power supply module 40, so that the intermittent energy-focused sound field generated by the energy focusing control unit is applied synchronously with the reverse polarization pulse. This synchronous application combines physical and electrochemical effects to efficiently strip the passivation layer or deposits on the electrode surface.

[0064] S600: After the reverse polarization pulse and the synchronously applied acoustic field effect end, the system automatically switches back to the forward oxidation working state of step S200 and begins the next pollutant degradation working cycle. The treated water that meets the standards is discharged through the outlet of reactor shell 10. The entire water purification method achieves efficient and continuous purification of water by repeatedly executing the cycle of pollutant degradation to online electrode regeneration.

[0065] In this embodiment of the invention, the degradation of pollutants in the water to be treated is achieved through the close synergistic action of multiple modules such as the anode module 20, the cathode module 30, and the sound field generation module 50.

[0066] At the anode module 20, pollutants undergo a multi-stage degradation process from physical capture to electrochemical oxidation. First, as the water to be treated flows through the three-dimensional porous structure of the anode module 20, the three-dimensional porous conductive substrate unit inside physically filters and intercepts suspended particulate matter in the water. Subsequently, dissolved organic pollutant molecules are adsorbed and enriched by the three-dimensional graphene network unit coated on the substrate surface. Under the positive oxidation potential applied by the DC power module 40, the manganese dioxide nanocatalytic layer unit loaded on the graphene surface oxidizes and degrades the enriched pollutants (denoted as R) through two pathways: one is direct electron transfer, where pollutant molecules lose electrons at catalytically active sites and are directly oxidized into intermediate products or inorganic substances; the other is indirect oxidation, where the manganese dioxide nanocatalytic layer unit catalyzes the discharge of surrounding water molecules (H2O) to generate highly oxidizing hydroxyl radicals (·OH), which then non-selectively oxidize the pollutants.

[0067] The degradation pathway at anode module 20 can be represented as follows: Direct electron transfer: R→R o x+ne - ; Indirect oxidation: H₂O → ·OH + H₂ + +e- ; Pollutant degradation: R + ·OH → degradation products; At the cathode module 30, a photoelectric Fenton synergistic oxidation process is simultaneously carried out, constructing the second strong oxidation core within the system. Under the cathode potential applied by the DC power supply module 40, dissolved oxygen (O2) in the water undergoes a two-electron oxygen reduction reaction on the cathode surface, generating hydrogen peroxide (H2O2) in situ and continuously as an intermediate product. Simultaneously, visible light emitted from the light source module 60 excites the Z-type heterojunction semiconductor catalytic layer unit to generate and separate highly active photogenerated electrons and holes. Following this, the in-situ Fenton catalytic central unit (using Fe...)... 3+ / Fe 2+ (Taking a cycle as an example) The in-situ generated H2O2 undergoes a Fenton-like reaction, efficiently decomposing it into hydroxyl radicals (·OH). The Fe consumed in this Fenton-like reaction... 2+ It can be achieved through the electrons provided by the cathode potential and the action of photogenerated electrons, by Fe 3+ Rapid reduction and regeneration enable continuous cycling of the Fenton catalyst, ensuring stable production of hydroxyl radicals.

[0068] The synergistic degradation pathway at cathode module 30 can be represented as follows: Hydrogen peroxide is generated: O2 + 2H + +2e - →H2O2; Fenton-like reaction: Fe 2+ +H₂O₂→Fe 3+ +·OH+OH - ; Catalyst regeneration: Fe 3+ +e - →Fe 2+ Pollutant degradation: R + ·OH → degradation products Throughout the reaction, the ultrasonic acoustic field generated by the acoustic field generation module 50 provides continuous physical enhancement to the aforementioned electrochemical and photoelectrochemical reaction processes. The acoustic cavitation effect generated by ultrasound in the liquid produces a large number of instantaneously collapsing cavitation bubbles near the electrode surface, releasing high-speed microjets and shock waves. This physical effect violently disturbs and thins the mass transfer boundary layer at the electrode-solution interface, greatly promoting the mass transfer rate of pollutant molecules, intermediate products, and reactants such as dissolved oxygen from the bulk water to the catalytically active surfaces of the anode module 20 and cathode module 30, thereby significantly improving the pollutant degradation kinetics of the entire system.

[0069] In summary, the embodiments of the present invention integrate a multi-stage capture-to-oxidation mechanism of the anode, a photo-to-electricity-to-Fenton synergistic oxidation mechanism of the cathode, and a sound field mass transfer enhancement mechanism covering the entire domain within the same reactor shell 10, forming a multi-path, three-dimensional, and highly efficient pollutant synergistic degradation system.

[0070] In a preferred embodiment, the system further includes a coordination control unit, which may be integrated into the DC power module 40 or as a separate controller module.

[0071] The collaborative control unit is connected to the pulse control unit of the DC power supply module 40 and the energy focusing control unit of the sound field generation module 50. Its function is to achieve efficient online recovery of electrode activity and precisely control the synchronous application of reverse polarization pulses and intermittent energy-focused sound fields.

[0072] Specifically, when the system needs to perform online electrode regeneration, the coordination control unit issues a synchronization trigger command. Upon receiving this command, the pulse control unit immediately controls the DC power supply module 40 to output a reverse polarization pulse; simultaneously, the energy focusing control unit also immediately controls the sound field generating module 50 to start outputting a high-intensity ultrasonic sound field. The duration of the reverse polarization pulse is set to be exactly the same as the working duration of the intermittent energy-focusing sound field to ensure precise temporal overlap between the two actions.

[0073] The mechanism of this synergistic control method lies in the organic combination of electrochemical and physical effects. On the surface of the original anode module 20 (which acts as a temporary cathode during reverse polarization), the reverse polarization pulse induces electrochemical reduction of the passivation layer (e.g., metal oxide) accumulated on its surface. This process alters the chemical structure of the passivation layer, reducing its physical adhesion and bonding strength to the electrode surface. Simultaneously, the synchronously applied ultrasonic field, with its powerful physical impact force and microjets generated by the acoustic cavitation effect, efficiently mechanically peels off and washes away the passivation layer whose bonding strength has been weakened by electrochemical action, thereby removing it from the electrode surface.

[0074] Through the simultaneous and synergistic effect of electrochemical loosening and physical stripping, compared with applying the two treatment methods alone or sequentially, the embodiments of the present invention can remove the deactivated substances on the electrode surface more quickly and thoroughly, achieve deep restoration of electrode catalytic activity, and thus ensure the long-term stability and treatment efficiency of the entire high-efficiency water purification system.

Claims

1. A high-efficiency water purification system, characterized in that, include: Reactor shell; An anode module is disposed inside the reactor shell, and the surface of the anode module is loaded with an electrocatalyst for electrocatalytic oxidation and degradation of pollutants in the water; A cathode module is disposed at an interval from the anode module within the reactor shell. The surface of the cathode module is provided with a visible light responsive catalytic layer, which is used to coordinate electrochemical reactions and photocatalytic reactions to convert intermediate products generated in the electrochemical reactions into strong oxidizing substances. A DC power supply module is electrically connected to the anode module and the cathode module respectively, providing electrical energy to the anode module and the cathode module to drive the electrochemical reaction; A sound field generating module, coupled to the reactor shell, is used to generate an ultrasonic sound field within the reactor shell to enhance the electrochemical reaction process. A light source module is disposed inside the reactor shell and is used to provide light to the visible light responsive catalytic layer of the cathode module to stimulate photocatalytic activity.

2. The high-efficiency water purification system according to claim 1, characterized in that, The anode module includes: Three-dimensional porous conductive substrate unit, used as a framework for current conduction and a medium for physical filtration; Three-dimensional graphene network units are coated on the surface of the three-dimensional porous conductive substrate unit to adsorb and enrich pollutants and construct electron transport channels. Manganese dioxide nanocatalytic layer units are loaded on the surface of the three-dimensional graphene network unit, wherein the manganese dioxide nanocatalytic layer units constitute the electrocatalyst.

3. The high-efficiency water purification system according to claim 1, characterized in that, The cathode module includes: Z-type heterojunction semiconductor catalytic layer units constitute the visible light responsive catalytic layer, which is used to generate and separate highly active photogenerated electrons and holes under light irradiation; An in-situ Fenton catalytic center unit is disposed on the Z-type heterojunction semiconductor catalytic layer unit and is used to undergo a Fenton-like reaction with the intermediate products of the electrochemical reaction to generate hydroxyl radicals.

4. The high-efficiency water purification system according to claim 3, characterized in that, The Z-type heterojunction semiconductor catalytic layer unit is composed of graphitic carbon nitride and bismuth vanadate; the in-situ Fenton catalytic center unit is iron oxide nanoparticles supported on the surface of the Z-type heterojunction semiconductor catalytic layer unit.

5. The high-efficiency water purification system according to claim 1, characterized in that, The DC power supply module includes: The pulse control unit is used to control the DC power module to output periodic positive oxidation pulses and reverse polarization pulses.

6. The high-efficiency water purification system according to claim 1, characterized in that, The sound field generating module includes: An energy focusing control unit is used to control the sound field generating module to generate an intermittent energy-focused sound field.

7. The high-efficiency water purification system according to claim 5, characterized in that, Also includes: The collaborative control unit is used to control the sound field generation module and the DC power supply module to work together so that the intermittent energy-focusing sound field is applied synchronously with the reverse polarization pulse.

8. The high-efficiency water purification system according to claim 2, characterized in that, The three-dimensional porous conductive substrate unit is a foamed titanium substrate.

9. The high-efficiency water purification system according to claim 1, characterized in that, The anode module, under the action of the DC power module, oxidizes and degrades pollutants in water through two pathways: direct electron transfer and catalytic generation of hydroxyl radicals from water molecules.

10. A high-efficiency water purification system according to claim 3, characterized in that, The cathode module, under the synergistic effect of the DC power module and the light source module, generates hydrogen peroxide through an oxygen reduction reaction. The in-situ Fenton catalytic center unit then catalyzes the hydrogen peroxide to generate hydroxyl radicals, thereby synergistically oxidizing and degrading pollutants in the water.

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